Reactions of (N-phenylsalicylideneiminato)aluminium(III)di(μ -isopropoxo)di (isopropoxo) aluminium(III) with simple and internally functionallized oximes. Molecular structure of the penta-coordinated complex (2-acetylthiophenyloximato)bis(N-phenylsalicylideneiminato)aluminium(III)

Article abstract of DOI:10.1016/S0277-5387(03)00454-6

Reactions of bis(N-phenylsalicylideneiminato)aluminium(III)di(μ -isopropoxo)di(isopropoxo) aluminium(III), [C₆H₄O{CH= N(C₆H₅)}]₂Al(μ-OPrⁱ) ₂Al(OPrⁱ)₂ (1) with simple and internally functionallized oximes in 1:1 and 1:2 molar ratios in refluxing anhydrous benzene yield binuclear complexes of the type, [C₆H ₄O{CH=N(C₆H₅)}]₂Al(μ-OPr ⁱ)₂Al(ON=CRR′)(OPrⁱ) and [C ₆H₄O{CH=N(C₆H₅)}] ₂Al(μ-OPrⁱ)₂Al(ON=CRR′)2 [where R=R′=CH₃; R=CH₃, R′=C₄H ₃S-2, C₄H₃O-2 and C₅H ₄N-2], respectively containing aluminium(III) atoms in six- and four-coordination sites. All these binuclear complexes are characterised by elemental analysis, molecular weight measurements and spectroscopy [IR and NMR(¹H, ¹³C and ²⁷Al)]. Reaction of bis(N-phenylsalicylideneiminato)(isopropoxo)aluminium(III) with 2-acetylthiophenyloxime in 1:1 molar ratio in refluxing anhydrous benzene, yields a novel heteroleptic compound, [C₆H₄O{CH=N(C ₆H₅)}]₂Al{ON=C(CH₃)C ₄H₃S-2} (10). The crystal structure of [C ₆H₄O{CH=N(C₆H₅)}] ₂Al{ON=C(CH₃)C₄H₃S-2}·CH ₂Cl₂ shows five-coordination around the aluminium(III) atom.

Full text of DOI:10.1016/S0277-5387(03)00454-6

Polyhedron 22 (2003) 2943ꢁ2952
/
www.elsevier.com/locate/poly
Reactions of (N-phenylsalicylideneiminato)aluminium(III)di(m-
isopropoxo)di (isopropoxo)aluminium(III) with simple and internally
functionallized oximes. Molecular structure of the penta-coordinated
complex (2-acetylthiophenyloximato)bis(N-
phenylsalicylideneiminato)aluminium(III)
Nikita Sharma a, Amit K. Jain a, Rajnish K. Sharma a, Rakesh Bohra a,*,
John E. Drake b, Michael B. Hursthouse c, Mark E. Light c
a Department of Chemistry, University of Rajasthan, Jaipur 302004, India
b Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ont., Canada N9B 3P4
c Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK
Received 11 April 2003; accepted 1 July 2003
Abstract
Reactions of bis(N-phenylsalicylideneiminato)aluminium(III)di(m-isopropoxo)di(isopropoxo) aluminium(III), [C6H4O{CHꢀ
N(C6H5)}]2Al(m-OPri)2Al(OPri)2 (1) with simple and internally functionallized oximes in 1:1 and 1:2 molar ratios in refluxing
anhydrous benzene yield binuclear complexes of the type, [C6H4O{CHꢀ
N(C6H5)}]2Al(m-OPri)2Al(ONꢀCRR?)(OPri) and
[C6H4O{CHꢀ CRR?)2 [where RꢀR?ꢀCH3; RꢀCH3, R?ꢀC4H3S-2, C4H3O-2 and C5H4N-2],
N(C6H5)}]2Al(m-OPri)2Al(ONꢀ
/
/
/
/
/
/
/
/
/
respectively containing aluminium(III) atoms in six- and four-coordination sites. All these binuclear complexes are characterised by
elemental analysis, molecular weight measurements and spectroscopy [IR and NMR(1H, 13C and 27Al)]. Reaction of bis(N-
phenylsalicylideneiminato)(isopropoxo)aluminium(III) with 2-acetylthiophenyloxime in 1:1 molar ratio in refluxing anhydrous
benzene, yields a novel heteroleptic compound, [C6H4O{CHꢀ
[C6H4O{CHꢀN(C6H5)}]2Al{ONꢀC(CH3)C4H3S-2}×CH2Cl2 shows five-coordination around the aluminium(III) atom.
# 2003 Elsevier Ltd. All rights reserved.
/
N(C6H5)}]2Al{ONꢀ
/
C(CH3)C4H3S-2} (10). The crystal structure of
/
/
/
Keywords: N-phenylsalicylideneiminato; Isopropoxo; Aluminium(III) atoms; Molecular structures
1. Introduction
We have recently reported that the dinuclear complex
[C6H4O{CHꢀ
N(C6H5)}]2Al(m-OPri)2Al(OPri)2 (I) dis-
/
plays unsymmetrical geometry containing six- and
four-coordinated aluminium(III) atoms [1,2] rather
than the symmetrical five-coordinated structure found
in, [C6H4O{CHꢀ
/
N(C6H5)}] (OPri)Al(m-OPri)2Al(OPri)
[C6H4O{CHꢀN(C6H5)}].
/
* Corresponding author.
E-mail address: rkbohra@satyam.net.in (R. Bohra).
0277-5387/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0277-5387(03)00454-6

2944
N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ2952
/
Table 1
Synthetic and analytical data of [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2(ONꢀ
/
CRR?)(OPri) and [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(ONꢀ
/
CRR?)2
S.
No.
Reactants (g) *
Molar PriOH (g) Found
ratio (Calc.)
%Yield %OPri
% Al
%N
MW Found
(Calc.)
M.p.
(8C)
1
2
3
4
5
6
7
8
(a) 2.33 (g)
(b) {2-SC4H3C(CH3)ꢀ
(g)
/
NOH} 0.48 1:1
0.20 (0.20)
0.50 (0.51)
0.15 (0.17)
0.47 (0.49)
0.20 (0.21)
0.34 (0.37)
0.20 (0.21)
0.33 (0.35)
97.3
98.7
98.6
96.0
98.8
96.8
99.0
99.5
23.0
(23.2)
7.04
(7.07)
5.10
(5.49)
701 (764)
780 (845)
659 (748)
745 (813)
715 (759)
795 (835)
603 (696)
675 (708)
80
78
(a) 2.90 (g)
(b) {2-SC4H3C(CH3)ꢀ
(g)
/NOH} 1.20 1:2
13.0
(13.9)
6.23
(6.38)
6.06
(6.62)
(a) 2.03 (g)
74
(b) {2-OC4H3C(CH3)ꢀ
(g)
/NOH} 0.37 1:1
23.5
(23.7)
7.13
(7.22)
5.19
(5.61)
(a) 2.81 (g)
68
(b) {2-OC4H3C(CH3)ꢀ
(g)
/NOH} 1.03 1:2
13.9
(14.5)
6.36
(6.64)
6.68
(6.88)
(a) 2.40 (g)
120
125
60
(b) {2-NC5H4C(CH3)ꢀ
(g)
/NOH} 0.48 1:1
22.9
(23.3)
7.06
(7.11)
7.09
(7.37)
(a) 2.14 (g)
(b) {2-NC5H4C(CH3)ꢀ
(g)
/NOH} 0.85 1:2
13.9
(14.1)
6.26
(6.46)
9.87
(10.0)
(a) 2.34 (g)
(b) (CH3)2Cꢀ
/
NOH 0.25 (g)
1:1
1:2
24.6
(25.4)
7.61
(7.76)
5.97
(6.03)
(a) 2.04 (g)
(b) (CH3)2Cꢀ
135
/
NOH 0.43 (g)
16.2
7.17
7.04
(16.6)
(7.62)
(7.90)
* (a) [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(OPri)2, (b) RR?Cꢀ
NOH.
/
In order to examine whether the stable basic unit (I)
can survive further nucleophilic attack, we carried out
reactions with simple and internally functionallized
anhydrous benzene [1]. Infrared spectra were recorded
as Nujol mulls on a Nicolet Magna 550 spectrophot-
1
ometer in the range 4000ꢁ
/
400 cmꢂ1. H and 13C NMR
oximes [3ꢁ
/
5]. The nucleophilic substitution reactions
spectra were recorded on a JEOL FX90Q spectrometer
using TMS as an internal reference in CDCl3 and
CHCl3, respectively. 27Al NMR spectra were carried
out in toluene using aluminium nitrate as an external
reference in aqueous solution. Molecular weight mea-
surements were carried out by elevation in boiling point
using a Beckmann’s Thermometer (Einstellthermometer
n-Beckmann, Labortherm-N, Skalenwert, 0.01 K, made
in GDR) fitted in glass assembly (supplied by JSGW,
India) in anhydrous benzene.
are quantitative and the binuclear products are stable
exhibiting different coordination sites for the two
aluminium(III) atoms. We report herein the reactions
of [C6H4O{CHꢀ
N(C6H5)}]2Al(m-OPri)2Al(OPri)2 with
simple and internally functionallized oximes and the
molecular structure of a new penta-coordinated (2-
acetyl thiophenyl oximato) bis(N-phenylsalicylideneimi-
nato)aluminium(III) complex.
/
2. Experimental
2.1. Synthesis of [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
OPri)2Al{ONꢀ
/
C(CH3)C4H3S-2}2
All manipulations were carried out under strictly
anhydrous conditions. Solvents were purified and dried
according to standard procedures [6]. Aluminium iso-
propoxide was prepared as described in the literature [7].
Aluminium was estimated gravimetrically as the oxinate
[6]. Nitrogen and isopropanol were estimated as re-
Typically,
[C6H4O{CHꢀ
and (2-SC4H3C(CH3)ꢀ
benzene (Â60 ml) was refluxed for 4 h under a
fractionating column. The isopropanol formed in the
reaction was fractionated out azeotropically with ben-
zene. The progress as well as the completion of the
reaction was checked by the estimation of the liberated
isopropanol in the azeotrope by the oxidimetric method.
the
N(C6H5)}]2Al(m-OPri)2Al(OPri)2 (2.90 g)
NOH) (1.20 g) in anhydrous
reaction
mixture
containing
/
/
/
ported earlier [6]. The starting material [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(OPri)2 was prepared by the
reaction of aluminium isopropoxide with N-phenyl
salicylidene imine in 1:1 molar ratio in refluxing

N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ
/2952
2945
A yellow, clear solution was obtained. After stripping
off the excess solvent under reduced pressure, a shiny-
yellow foamy solid was obtained in quantitative yield,
which was recrystallized from benzene/hexane. The
complexes 1ꢁ/8 were prepared by a similar route and
the details are summarized in Table 1.
2.2. Synthesis of [C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri)
To a benzene solution (Â/35 ml) of aluminium
isopropoxide (3.72 g) was added {C6H4(OH)CHꢀ
/
N(C6H5)} (7.20 g) in benzene (30 ml). The contents
were refluxed for 4 h and the progress of the reaction
was monitored by the determination of isopropanol
liberated azeotropically with benzene. A yellow, clear
solution was obtained. After stripping off the solvent
under reduced pressure, a yellow solid was obtained in
quantitative yield; Anal. Found: Al, 5.33; N, 2.43%;
Calc. Al, 5.64; N, 2.92%.
2.3. Synthesis of [C6H4O{CHꢀ
/
N(C6H5)}]2Al{ONꢀ
/
C(CH3)C4H3S-2}
Typically, 2-acetylthiophenoxime (0.36 g) was added
to a benzene solution (Â40 ml) of [C6H4O{CHꢀ
/
/
N(C6H5)}]2Al(OPri) (1.20 g) and the reaction mixture
was refluxed on a fractionating column for 4 h. The
isopropanol in the reaction was collected azeotropically
with benzene. The progress as well as the completion of
the reaction was checked by the estimation of the
liberated isopropanol in the azeotrope by the oxidi-
metric method. A yellow, clear solution was obtained.
After stripping off the excess solvent under reduced
pressure, a shiny-yellow foamy solid was obtained in
quantitative yield which was recrystallized from a (7:1)
mixture of dichloromethane and n-hexane: Anal.
Found: Al, 4.79; N, 7.01%; Calc. Al, 4.82; N, 7.5%.
Analytical data of 9ꢁ/12 are summarized in Table 5.
2.4. X-ray diffraction analysis
A
colourless, plate crystal of [C6H4OCHꢀ
/
NC6H5]2Al{ONꢀC(CH3)C4H3S-2}×CH2Cl2 (10) was
/
/
mounted on a glass fibre. Cell dimensions and intensity
data were recorded on an Enraf Nonius KCCD
diffractometer, with f and v scans chosen to give a
complete asymmetric unit. The data collection and cell
refinement [8] gave cell constants corresponding to a
monoclinic cell whose dimensions are given in Table 10
along with other experimental parameters. An absorp-
tion correction was applied [9] which resulted in
transmission factors ranging from 0.9931 to 0.9341.
The structure was solved by direct methods [10], and the
structure was refined using the WINGX [11] version of
SHELX-97 [12]. All of the non-hydrogen atoms were
treated anisotropically. Hydrogen atoms were included

2946
N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ2952
/
Table 3
1H NMR spectra for [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(ONꢀ
/
CRR?)(OPri) and [C6H4O{CHꢀ
Isopropoxy moiety
/
N(C6H5)}]2 Al(m-OPri)2Al(ONꢀ
Oximate moiety
/CRR?)2
S.
No.
Compound
N-Phenylsalicylidene
imineto moiety
CHꢀ/N
Aromatic
proton
CH3
OCH
1
2
3
4
5
6
7
8
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
8.78,s
8.68,s
(2H)
7.16ꢁ
(18H)
/
7.79,m 1.26,d (12H) 3.93,m (2H)
1.83,d (6H) 4.24,m (1H)
2.29,s(3H,CH3); 6.97,d(1H,H-4);
7.03,d(1H,H-3); 7.10(1H,H-5)
OPri)2Al{ONꢀ
2}(OPri)
/
C(CH3)C4H3S-
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C4H3S-2}2
8.78,s
8.68,s
(2H)
7.22ꢁ
/
7.98,m 1.33,d (12H) 4.10,m (2H)
2.21,s(3H,CH3); 6.84,d(1H,H-4);
6.97,d(1H,H-3); 7.03(1H,H-5)
OPri)2Al{ONꢀ
/
(18H)
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C4H3O-
8.78,s
8.68,s
(2H)
7.22ꢁ
/
7.60,m 1.26,d (12H) 3.86,m (2H)
4.24,m (1H)
2.09,s(3H,CH3); 6.40,d(1H,H-4);
6.72,d(1H,H-3); 7.16(1H,H-5)
OPri)2Al{ONꢀ
2}(OPri)
/
(18H)
1.96,d (6H)
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C4H3O-2}2
8.78,s
8.68,s
(2H)
7.00ꢁ
/
7.54,m 1.20,d (12H) 3.77,m (2H)
2.18,s(3H,CH3); 6.68,d(1H,H-4);
6.78,d(1H,H-3); 6.87(1H,H-5)
OPri)2Al{ONꢀ
/
(18H)
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C5H4N-
8.52,s
8.46,s
(2H)
6.53ꢁ
/
7.38,m 1.23,d (12H) 3.86,m (2H)
1.48,d (6H)
2.21,s(3H,CH3); 7.44,t(1H,H-4);
7.51,t(1H,H-3); 7.70,t (1H,H-5);
8.05,d(1H,H-6)
OPri)2Al{ONꢀ
2}(OPri)
/
(18H)
4.15,m (1H)
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C5H4N-2}2
8.87,s
8.81,s
(2H)
6.65ꢁ
/
7.32,m 1.20,d (12H) 4.05,m (2H)
2.15,s(3H,CH3); 7.44,t(1H,H-4);
7.57,t(1H,H-3); 7.73,t (1H,H-5);
7.79,d(1H,H-6)
OPri)2Al{ONꢀ
/
(18H)
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
8.90,s
8.84,s
(2H)
6.78ꢁ
/
7.48,m 1.33,d (12H) 3.86,m (2H)
1.94,d (6H)
1.96,s(6H,CH3)
OPri)2Al{ONꢀ
/
C(CH3)2}(OPri)
(18H)
4.37,m (1H)
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)2}2
8.71,s
8.65,s
(2H)
6.62-7.48,m 1.17,d (12H) 4.02,m (2H)
(18H)
1.83,s(6H,CH3)
OPri)2Al{ONꢀ
/
in idealized positions with isotropic thermal parameters
set at 1.2 times that of the carbon atom to which they
were attached. The final cycle of full-matrix least-
squares refinement was based on 6945 observed reflec-
meters and converged (largest parameter shift was 0.001
times its esd).
Selected distances and bond angles are given in Table
9 and the molecule is displayed in the ORTEP diagram in
Fig. 4. Additional material available from the Cam-
tions (3461 for F2 ꢀ4s(F2)) and 390 variable para-
/
Table 4
13C NMR spectra for [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(ONꢀ
/
CRR?)(OPri)and [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(ONꢀ
CRR?)2
/
S.
No.
Compound
N-Phenylsalicylidene imineto moiety
Isopropoxy
moiety
Oximate moiety
CHꢀ
/
N
Aromatic carbon
CH3
OCH
1
2
3
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
161.2;
C(CH3)C4H3S-2}(OPri) 162.6
117.2; 118.9; 119.2; 121.2; 123.4; 24.9;
124.0; 125.6; 127.9; 133.1; 135.2 25.3
117.3; 119.0; 120.2; 121.2; 123.8; 25.4
124.0; 125.9; 128.3; 132.2; 133.8
62.1;
64.4
62.2
11.9(CH3); 126.6(C4); 126.8(C3);
127.0(C5); 140.4 (C2); 151.4(CꢀN)
12.1(CH3); 126.4 (C4); 126.8(C3);
127.4(C5); 140.2(C2); 151.6(CꢀN)
11.2(CH3); 109.3(C4); 112.1(C3);
143.4(C5); 147.9 (C2); 151.4(CꢀN)
OPri)2Al{ONꢀ
/
/
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C4H3S-2}2
162.6;
162.7
161.2;
162.7
OPri)2Al{ONꢀ
[{C6H4O{CHꢀ
/
/
/
N(C6H5)}]2Al(m-
C(CH3)C4H3O-
117.2; 118.7; 119.3; 121.9; 124.3; 23.5;
125.6; 127.9; 128.3; 134.1; 135.0 25.8
63.9;
64.1
OPri)2Al{ONꢀ
2}(OPri)
/
/
4
5
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
161.3;
162.1
162.6;
162.8
117.5; 118.9; 121.9; 123.9; 124.0; 24.8
124.9; 125.9; 127.9; 132.9; 135.9
64.1
11.0(CH3); 109.9(C4); 111.9(C3);
143.3(C5); 146.9(C2); 150.9(CꢀN)
10.2(CH3); 123.6(C5); 124.4 (C3);
OPri)2Al{ONꢀ
[{C6H4O{CHꢀ
/
C(CH3)C4H3O-2}2
/
/
N(C6H5)}]2Al(m-
117.2; 119.0; 121.1; 124.9; 126.9; 23.9;
128.1; 128.3; 129.4; 132.2; 133.1 25.3
62.5;
64.1
OPri)2Al{ONꢀ
2}(OPri)
/
C(CH3)C5H4N-
137.5(C4); 148.8(C6); 153.1(C2);
156.9(CꢀN)
/
6
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
C(CH3)C5H4N-2}2
162.9;
163.3
117.9; 119.3; 121.4; 124.9; 126.7; 25.2
128.3; 128.9; 129.5; 132.4; 134.9
64.3
10.0(CH3); 123.5(C5); 126.1(C3);
135.2(C4); 149.2(C6); 153.2(C2);
OPri)2Al{ONꢀ
/
157.3(Cꢀ
11.7(CH3); 159.9(Cꢀ
/
N)
7
8
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-
161.5;
162.1
161.2;
162.9
117.4; 119.3; 121.7; 123.0; 124.9; 23.7;
126.5; 128.9; 132.7; 133.1; 135.4 25.1
117.4; 119.3; 121.7; 123.0; 124.9; 24.9
126.5; 128.9; 132.7; 133.1; 135.4
63.6;
64.6
64.1
/N)
OPri)2Al{ONꢀ
[{C6H4O{CHꢀ
/
C(CH3)2}(OPri)
/
N(C6H5)}]2Al(m-
11.4(CH3); 160.7(Cꢀ
/N)
OPri)2Al(ONꢀ
/C(CH3)2}2

N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ
/2952
2947
Table 5
Synthetic and analytical data of [C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri) and [C6H4O{CHꢀ
Molar ratio PriOH (g) Found (Calc.) %Yield %Al
/
N(C6H5)}]2Al(ONꢀCRR?)
/
S. No. Reactants (g) a,b
%N
MW Found (Calc.)
9
(a) Al(OPri)3, 3.72 (g)
(b) {C6H4(OH)CHꢀN(C6H5)}, 7.20 (g) 1:2
/
2.01 (2.18)
0.15 (0.15)
0.21 (0.21)
0.18 (0.19)
100
99
5.33 (5.64) 2.43 (2.92) 440 (479)
4.79 (4.82) 7.01 (7.50) 512 (560)
4.83 (4.86) 7.42 (7.57) 523 (555)
4.81 (4.96) 7.04 (7.72) 509 (544)
10
11
12
(a) 1.20 (g)
(b) {2-SC4H3C(CH3)ꢀ
/
NOH}, 0.36 (g)
1:1
(a) 1.70 (g)
(b) {2-NC5H4C(CH3)ꢀ
/
NOH}, 0.48 (g) 1:1
99
(a) 1.51 (g)
(b) {2-OC4H3C(CH3)ꢀ
/NOH}, 0.39 (g)
1:1
98
a
[C6H4O{CHꢀ
RR?CꢀNOH.
/
N(C6H5)}]2Al(OPri).
b
/
bridge Crystallographic Data Centre comprises the final
atomic coordinates for all atoms, thermal parameters
and a complete listing of bond distances and angles.
cular weight determinations indicate the binuclear
nature of these complexes in refluxing anhydrous
benzene (Table 1).
3. Results and discussion
3.2. IR Spectra
Tentative assignments of significant bands are sum-
3.1. Preparation
marized in Table 2. The broad stretching bands at Â
3300 cmꢂ1 due to the ꢁ
OH groups of the free ligands do
not appear in the IR spectra of the above derivatives
indicating the deprotonation of the ꢁOH groups and the
formation of AlꢁO bonds. This is supported by the
appearance of a new band in the region 655ꢁ
680 cmꢂ1
assigned to n(AlꢁO) [13]. Coordination of N-phenylsa-
/
The reactions of [C6H4O{CHꢀN(C6H5)}]2Al(m-
/
/
OPri)2Al(OPri)2 with simple as well as internally func-
tionallized oximes in 1:1 and 1:2 molar ratios in
refluxing anhydrous benzene solution yield the desired
products:
/
/
/
[C6H4OfCHꢀN(C6H5)g]2Al(m-OPri)2Al(OPri)2
/
licylideneimine to aluminium through the azomethine
ꢃnRR?CꢀNOH 0
nitrogen atom is expected to reduce the electron density
[C6H4OfCHꢀN(C6H5)g]2
in the azomethine link and lower the n(Cꢀ
frequency. In the spectra of all of the new complexes, the
band due to n(CꢀN) appears at lower wave-number,
1610ꢁ
1620 cmꢂ1, indicative of coordination of the
/N) absorption
Al(m-OPri)2Al(ONꢀCRR?)n(OPri)2ꢂn
ꢃnPriOH
/
/
[where Rꢀ
/
R?ꢀ
/
CH3; Rꢀ
/
CH3, R?ꢀC4H3S-2, C4H3O-
/
azomethine nitrogen to the aluminium atom [14,15].
This is supported by the appearance of a new band at
2 and C5H4N-2 and nꢀ/1 or 2]
All of these reactions are quantitative and the
liberated isopropanol could be removed readily in 4 h.
Their completion was checked by estimating the iso-
propanol liberated azeotropically. All of the products
are yellow, foamy solids that are soluble in common
organic solvents and show sharp melting points. Mole-
600ꢁ
intensity band observed in the region 998ꢁ
assigned to n(CꢁO) in the isopropoxy group. The Alꢁ
OꢁAl vibrations are observed in the region 740ꢁ760
cmꢂ1
/
640 cmꢂ1 assigned to n(Alꢁ
/
N) [13]. The medium
/
1010 cmꢂ1 is
/
/
/
/
.
Table 6
IR spectra for [C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri) and [C6H4O{CHꢀ
N-Phenylsalicylidene imineto moiety Oximate moiety n(Nꢁ
n(CꢀC) n(CꢀN) n(CꢁO)
/
N(C6H5)}]2Al(ONꢀ
/
CRR?)2
S.
No.
Compound
/
O) n(Alꢁ
/
N) n(AlꢁO)
/
/
/
/
9
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri)
1470m
C(CH3)C4H3S-2} 1470m
C(CH3)C5H4N-2} 1480m
1610s
1615s
1610s
1620s
1200m
1230m
1250m
1250m
1375m
1325m
1325m
1375m
610m
630m
605m
610m
695m
695m
670m
680m
10 [{C6H4O{CHꢀ
11 [{C6H4O{CHꢀ
12 [{C6H4O{CHꢀ
/
N(C6H5)}]2Al{ONꢀ
N(C6H5)}]2Al{ONꢀ
N(C6H5)}]2Al{ONꢀ
/
/
/
/
/C(CH3)C4H3-2}
1475m

2948
N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ2952
/
Table 7
1H NMR spectra for [C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri) and [C6H4O{CHꢀ
/
N(C6H5)}]2Al(ONꢀ/CRR?)
S.
No.
Compound
N-Phenylsalicylidene imineto
moiety
Isopropoxy moiety
Oximate moiety
CHꢀ/N
Aromatic pro-
tons
CH3
OCH
9
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri)
8.68, s 8.65, s 6.47ꢁ
(2H) (18H)
8.68, s 8.62, s 7.25ꢁ
(2H) (18H)
8.78, s 8.72, s 6.91ꢁ
(2H) (18H)
/
7.86, m
7.48, m
7.67, m
1.03, d
(6H)
3.40, m
(1H)
ꢁ/
10
11
[{C6H4O{CHꢀ
C(CH3)C4H3S-2}
[{C6H4O{CHꢀN(C6H5)}]2Al{ONꢀ
C(CH3)C5H4N-2}
/
N(C6H5)}]2Al{ONꢀ
/
/
ꢁ/
ꢁ/
2.21, s(3H,CH3); 6.81, d(1H,H-4);
6.97, d(1H,H-3); 1.16(1H,H-5)
2.20, s(3H,CH3); 7.50, t(1H,H-4);
7.53, t(1H, H3); 7.72(1H,H5); 8.21,
d(1H,H-6)
/
/
/
ꢁ/
ꢁ/
12
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al{ONꢀ
/
8.78, s 8.68, s 6.98ꢁ
(2H) (18H)
/
7.59, m
ꢁ/
ꢁ/
2.04, s(3H,CH3); 1.42, d(1H,H-4);
6.80, d(1H,H-3); 8.21(1H,H-5)
C(CH3)C4H3O-2}
3.3. 1H NMR spectra
protons, respectively, of the bridging and terminal
isopropoxy groups (for compounds 1, 3, 5 and 7),
indicate the nonequivalent nature of bridging and
terminal isopropoxy groups. Aromatic protons of N-
phenylsalicylidene imine are observed in the region d
The important signals in the 1H NMR spectra of these
derivatives are summarized in Table 3. Comparison of
the spectra of the free oximes with the spectra of the
corresponding derivatives shows the absence of signals
6.53ꢁ7.98 ppm as a multiplet [1].
/
attributable to ꢁ
the OH groups of the oxime ligands and the formation
of AlꢁO bonds. This is supported by the significant
/
OH, indicating the deprotonation of
3.4. 13C NMR spectra
/
shifting of the positions of the methyl signals of the
ligand moiety. However, no appreciable shift was
observed in the positions of the ring protons of the
functionallized oximes ruling out the possibility of
coordination through the hetero (N, O or S) atom
[16]. The presence of two singlet for the azomethine
proton signals of the N-phenylsalicylideneimine group
in the spectra of all these complexes, indicates the
nonequivalent nature of azomethine protons. These
signals are downfield compared to the free Schiff’s
base, suggesting deshielding of the azomethine protons
due to coordination to aluminium through the azo-
methine nitrogen [1]. Similarly, the presence of two
doublets and two multiplets for the methyl and methine
The mode of bonding suggested above is confirmed
by the 13C NMR spectra (Table 4). The Cꢀ
/
N signal of
the internally functionalized oximes in general is de-
shielded as compared to its position for the correspond-
ing free oximes, indicating the formation the Alꢁ
/O
bond. The carbon signals due to the heterocyclic ring of
the functionallized oximes do not show any shifting
after complexation, indicating that the hetero (N, O or
S) atom is not taking part in bonding with aluminium.
The azomethine (ꢀ
two signals appear at 161.2ꢁ
/
CHꢀ
/
N) carbon is deshielded and
/
162.9 and 162.1ꢁ163.32
/
ppm. This deshielding, as well as the presence of two
carbon signals, provides further support of coordination
through the azomethine nitrogen to the aluminium atom
Table 8
13C NMR spectra for [C6H4O{CHꢀ
/
N(C6H5)}]2Al(OPri) and [C6H4O{CHꢀ
N-Phenylsalicylidene imineto moiety
/
N(C6H5)}]2Al(ONꢀCRR?)
/
S.
No.
Compound
Isopropoxy
moiety
Oximate moiety
CHꢀ/N
Aromatic carbon
CH3
OCH
9
[{C6H4O{CHꢀ
/
N(C6H5)}]2Al(O-
165.2;
168.1
162.8;
163.1
117.2; 118.9; 119.2; 121.2; 123.4; 24.8;
124.0; 125.6; 127.9; 133.1; 135.2 25.4
63.7;
65.2
ꢁ
/
Pri)
10
[{C6H4O{CHꢀ
N(C6H5)}]2Al{ONꢀ
C(CH3)C4H3S-2}
[{C6H4O{CHꢀ
N(C6H5)}]2Al{ONꢀ
C(CH3)C5H4N-2}
[{C6H4O{CHꢀ
N(C6H5)}]2Al{ONꢀ
C(CH3)C4H3O-2}
/
117.3; 119.0; 120.2; 121.2; 123.8;
124.0; 125.9; 128.3; 132.2; 133.8
ꢁ/
ꢁ/
12.4(CH3); 126.3(C4); 126.7(C3);
127.5(C5); 140.9(C2); 151.9(CꢀN)
/
/
11
12
/
162.7;
162.9
117.2; 118.7; 119.3; 121.9; 124.3;
125.6; 127.9; 128.3; 134.1; 135.0
ꢁ/
ꢁ/
10.9(CH3); 123.5(C5); 124.8(C3);
137.5(C4); 149.2(C6); 153.4(C2);
/
157.2(Cꢀ
11.2(CH3); 109.1(C4); 112.3(C3);
144.2(C5); 147.7(C2); 152.3(CꢀN)
/N)
/
161.8;
162.2
117.5; 118.9; 121.9; 123.9; 124.0;
124.9; 125.9; 127.9; 132.9; 135.9
ꢁ/
ꢁ/
/
/

N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ
/2952
2949
Table 9
Selected bond lengths (A) and angles (8) for [C6H4OCHꢀ
NC6H5]2Al{ONꢀC(CH3)C4H3S-2}×CH2Cl2
3.5. 27Al NMR spectra
˚
/
27Al NMR spectra of compounds, [C6H4O{CHꢀ
N(C6H5)}]2Al(m-OPri)2Al{ONꢀC(CH3)C4H3S-2}(OPri)
[A], [C6H4O{CH ꢀ
N(C6H5)}]2Al(m-OPri)2Al{ON ꢀ
C ( C H 3 ) C 4 H 3 S - 2 } 2 [ B ] a n d [ C 6 H 4 O { C H ꢀ
C(CH3)C5H4N-
/
/
/
/
Bond lengths
Al(1)ꢁ
Al(1)ꢁ
Al(1)ꢁ
/
O(1)
O(2)
N(2)
1.759(2)
1.760(2)
2.057(2)
Al(1)ꢁ
Al(1)ꢁ
Al(1)ꢁ
/
N(1)
O(3)
N(3)
2.737(3)
1.758(2)
2.039(2)
/
/
/
/
/
/
/
N(C6H5)}]2Al(m-OPri)2Al{ON ꢀ
/
2}(OPri) [C] at room temperature exhibit two signals at
d 7.4 (linewidths 132.03 Hz), 7.6 (linewidths 100.35 Hz),
7.9 (linewidths 155.25 Hz) ppm and d 54.1 (linewidths
176.04 Hz), 55.4 (linewidths 167.26 Hz), 53.1 (linewidths
186.31 Hz) ppm, respectively indicating the presence of
both six- and four-coordination around the two alumi-
nium atoms [2] (Fig. 1).
Bond angles
N(1)ꢁAl(1)ꢁ
O(1)ꢁAl(1)ꢁ
O(1)ꢁAl(1)ꢁ
O(2)ꢁAl(1)ꢁ
O(3)ꢁAl(1)ꢁ
Al(1)ꢁO(2)ꢁ
C(13)ꢁN(2)ꢁ
Al(1)ꢁO(1)ꢁN(1)
/
/
N(3)
174.5(1)
117.7(1)
86.14(9)
89.2(1)
O(1)ꢁ
O(2)ꢁ
O(1)ꢁ
O(2)ꢁ
O(3)ꢁ
Al(1)ꢁ
C(26)ꢁ
O(1)ꢁAl(1)ꢁ
/
Al(1)ꢁ
Al(1)ꢁ
Al(1)ꢁ
Al(1)ꢁ
Al(1)ꢁ
O(3)ꢁ
N(3)ꢁ
N(1)
/
O(2)
O(3)
N(3)
N(3)
N(3)
C(20)
119.9(1)
122.3(1)
98.6(1)
85.9(1)
89.8(1)
129.0(2)
123.6(2)
25.9(1)
/
/
O(3)
N(2)
N(2)
N(2)
C(7)
/
/
/
/
/
/
/
/
/
/
/
/
90.61(9)
131.0(2)
121.1(2)
120.5(2)
/
/
/
/
/
/
/
/
Al(1)
/
/Al(1)
/
/
/
/
In view of the dinuclear nature of products 1ꢁ8 as
/
well as the monodentate behaviour of the simple and
internally functionallized oximes as indicated by the
above studies, the following tentative structure may be
proposed for these derivatives (Fig. 2).
and the nonequivalent nature of azomethine carbon.
The aromatic carbon signal of N-phenylsalicylidenei-
mine appears in the range d 117.2ꢁ135.9 ppm. Further,
/
From the above studies it appears that binuclear
unsymmetrical structures containing aluminium(III)
atoms in six- and four-coordination states, e.g.
the presence of two carbon signals each for methyl and
methine of the isopropoxy groups in compounds 1, 3, 5
and 7, indicate that bridging and terminal isopropoxy
groups are magnetically nonequivalent.
[C6H4O{CHꢀ
N(C6H5)}]2Al(m-OPri)2Al(OPri)2, are rela-
tively more stable compared to the symmetrical dimeric
/
structure containing aluminium(III) atoms in five-co-
N(C6H5)}](OPri)Al(m-
ordination states, [C6H4O{CHꢀ
/
OPri)2Al[C6H4O{CHꢀN(C6H5)}](OPri).
/
It is rather difficult to explain why four- and six-
coordinate geometries are favoured over symmetrical
five-coordinate structures. A possible explanation could
be that the b-diketone chelates exert a marked pre-
ference for spanning tetra- and hexa-coordinated alu-
minium sites and avoid participation in five-coordinate
geometries. However, it is difficult to rule out the
Table 10
Crystal data and structure refinement for [C6H4OCHꢀ
NC6H5]2Al{ONꢀ
/
/
C(CH3)C4H3S-2}×CH2Cl2
/
Empirical formula
Formula weight
Temperature (8C)
Wavelength (A)
Crystal system
Space group
C33H28N3O3AlSCl2
644.52
153(2)
ꢂ
/
˚
0.71073
monoclinic
P21/c
˚
a (A)
14.7261(5)
9.3110(3)
22.6595(10)
95.9330(10)
3090.3(2)
4
˚
b (A)
˚
c (A)
b (8)
3
V (A )
˚
Z
Dcalc (g cmꢂ3
Absorption coefficient (mmꢂ1
F(0 0 0)
)
1.385
0.346
1336
)
Crystal size (mm)
u Range for data collection (8)
Index ranges
0.20ꢄ
3.08ꢁ27.50
19 h 17, ꢂ
/
0.20ꢄ
/
0.02
10 k 11, ꢂ
0.0819]
/
ꢂ/
/
/29 l 24
Reflections collected
Independent reflections
Max./min. transmission
Refinement method
17 092
6945 [Rint
ꢀ/
0.9931 and 0.9341
Full-matrix least-squares on
F2
Data/restraints/parameters
Goodness-of-fit on F2
6945/0/390
0.937
Final R indices [F2ꢀ
R indices (all data)
Extinction coefficient
/
4s(F2)]
R1ꢀ
R1ꢀ
0.0004(4)
0.734 and ꢂ0.321
/0.0568, wR2ꢀ
/
0.1027
/0.1493, wR2ꢀ
/
0.1291
Largest difference peak and hole
3
/
(eꢂ A )
˚
Fig. 1. 27Al NMR spectra of [A], [B] and [C] at room temperature.

2950
N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ2952
/
cmꢂ1 can be assigned to n(Alꢁ
and the lowering (Â
20 cmꢂ1) of the n(Nꢁ
vibrations in all complexes further supports the forma-
tion of AlꢁO bonds. The bidentate nature of the N-
phenylsalicylideneimine moiety in these compounds is
/
O) stretching vibrations
O) stretching
/
/
/
supported by the presence of strong (1610ꢁ
and medium (1470ꢁ
1480 cmꢂ1) bands due to n(Cꢀ
and n(CꢀC), respectively.
/
1620 cmꢂ1
)
N)
/
/
/
3.7. 1H NMR spectra
Fig. 2. Proposed structure of [C6H4O{CHꢀ
OPri)2Al(ONꢀCRR?)n(OPri)2ꢂn [where Lꢀ
L’ꢀRR?Cꢀ
OPri and L’ꢀ
RR?CꢀNOH; RꢀR?ꢀCH3; RꢀCH3, R?ꢀ
C4H3O-2 and C5H4N-2 and nꢀ1 or 2].
/
NC6H5}]2 Al(m-
NOH; Lꢀ
C4H3S-2,
/
/
/
/
/
/
/
/
/
/
/
A comparison of the spectra of the free oximes with
the spectra of the corresponding derivatives again shows
/
the absence of ꢁ
the OH groups of the free oxime ligands and the
formation of AlꢁO bonds (Table 7). This is supported
by the significant shifting of the positions of the methyl
signals of the ligand moiety. However, no appreciable
shift was observed in the positions of the ring protons of
the functionallized oximes ruling out the possibility of
coordination through the N, O or S atom.
The presence of two singlet for the azomethine proton
signals of the N-phenylsalicylideneimine group in the
spectra of all these complexes, indicates the nonequiva-
lent nature of the azomethine protons. A multiplet in the
/
OH signals indicating deprotonation of
possibility that five-coordinate intermediates are formed
in the synthesis of many of these compounds, and that
these rapidly rearrange to the observed products con-
taining four- and six-coordinated aluminium atom. In
view of this, the preparation of monomeric heteroleptic
Al(III) derivatives containing penta- coordinated Al(III)
atoms were attempted using some sterically crowded
ligands.
/
The reaction of Al(OPri)3 with [C6H4(OH)CHꢀ
/
N(C6H5)}] in 1:2 molar ratio in anhydrous benzene
yields the aluminium(III) complex:
Al(OPri)3 ꢃ2[C6H4(OH)CHꢀN(C6H5)g]
0 [C6H4OfCHꢀN(C6H5)g]2Al(OPri)
ꢃ2PriOH
region d 6.47ꢁ7.86 ppm is assigned to the aromatic
/
protons of N-phenylsalicylideneimine moiety.
3.8. 13C NMR spectra
This reaction is quite facile and quantitative. The
product was characterized by elemental analysis and IR
and NMR spectroscopy.
In the 13C NMR spectra of all these complexes, the
Cꢀ
position in the corresponding free oximes, indicating the
formation of the AlꢁO bond (Table 8). The carbon
/N signal in general is deshielded as compared to its
Further reactions of [C6H4O{CHꢀ
/
N(C6H5)}]2Al(O-
Pri) with internally functionallized oximes in 1:1 molar
ratio in refluxing anhydrous benzene give products of
the following type:
/
signals due to the heterocyclic ring of the functionallized
oximes are observed at their expected positions indicat-
ing that the heteroatom (O, N or S) does not take part in
[C6H4OfCHꢀN(C6H5)g]2Al(OPri)
bonding with aluminium. The azomethine (ꢀ
carbon is deshielded and two signals appear in the
region d 161.8ꢁ168.1 ppm. This deshielding, as well as
/
Cꢀ/N)
ꢃRR?CꢀNOH
0 [C6H4OfCHꢀN(C6H5)g]2Al(ONꢀCRR?)
/
ꢃPriOH
the presence of the two carbon signals, supports
coordination through the azomethine to the aluminium
atom and the nonequivalent nature of the azomethine
carbon atom. The azomethine carbon signals of N-
(where Rꢀ
/
CH3; R?ꢀC4H3S-2, C4H3O-2, C5H4N-2)
/
These reactions are quite facile and quantitative. All
these derivatives are yellow coloured solids, hygroscopic
in nature and are soluble in common organic solvents.
Molecular weight measurements indicate their mono-
meric nature in refluxing anhydrous benzene.
phenylsalicylideneimine appear in the range d 115.2ꢁ
/
151.4 ppm.
3.9. 27Al NMR spectra
3.6. IR spectra
The 27Al NMR spectrum at room temperature of a
representative derivative, [C6H4O{CHꢀ
/
N(C6H5)}]2-
The broad stretching vibrations at Â
to the ꢁOH groups of the free oximes are not present in
the IR spectra of these derivatives suggesting the
deprotonation of the ꢁOH group and the formation of
AlꢁO bonds (Table 6). Bands in the region 670ꢁ690
/
3300 cmꢂ1 due
Al{ONꢀC(CH3)C4H3S-2}, (10) exhibits a hump at d
/
/
26.9 ppm indicating the presence of penta-coordination
around the aluminium atom.
In view of the mononuclear nature of the above
products as well as the monodentate behaviour of the
/
/
/

N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ
/2952
2951
nitrogen atoms of the N-phenylsalicylideneimine ligands
N bite-angles of 89.8(1)8 and 89.2(1)8
which are similar to those found for the same ligands,
resulting in Oꢁ
/
Alꢁ
/
89.5(1)8 and 88.7(1)8, in the six-coordinate aluminium
environment found in [C6H4O{CHꢀ
OPri)2Al(OPri)2 [1]. The bite-angles accommodate the
cis ꢁtrans arrangement in octahedral as readily as
equatorial-axial in trigonal bipyramidal. The N(2)ꢁ
Al(1)ꢁN(3) angle of 174.5(1)8 for the axial positions in
10, is closer to 1808 than the N(1)ꢁAl(1)ꢁN(2) trans
N(C6H5)}]2Al(m-
/
N(C6H5)}]2Al(m-
/
/
Fig. 3. Proposed structure of [C6H4O{CHꢀ
/
NC6H5}]2 Al (ONꢀCRR?)
/
/
[where RꢀCH3, R?ꢀC4H3S-2, C4H3O-2 and C5H4N-2].
/
/
/
/
angle of 169.4(1)8 in [C6H4O{CHꢀ
/
internally functionallized oximes as indicated by the
above studies, the following tentative structure may be
proposed for these derivatives (Fig. 3).
OPri)2Al(OPri)2. Comparable bond lengths in the five-
coordinate environment of aluminium in 10 are
shorter than those in the six-coordinate environment
The single crystal X-ray diffraction of the complex
C(CH3)C4H3S-2},
in [C6H4O{CHꢀ
/
N(C6H5)}]2Al(m-OPri)2Al(OPri)2, with
[C6H4O{CHꢀ
/
N(C6H5)}]2Al{ONꢀ
/
AlꢁO and AlꢁN bond lengths averaging 1.759(1) and
/
/
supports the inference drawn by the above studies that
in these monomeric complexes the coordination number
around the aluminium(III) atom is five.
˚
2.048(13) A respectively in 10 and 1.816(4) and 2.077(3)
A
in [C6H4O{CHꢀ
The Al(1)ꢁ
/
N(C6H5)}]2Al(m-OPri)2Al(OPri)2.
O(1) oxime bond of 1.759(2) A in 10 is
˚
˚
/
identical to those of the Alꢁ
phenylsalicylideneiminato ligands. However, the intera-
/O bonds to the bidentate N-
3.10. Molecular structure of [C6H4O{CHꢀ
/
tomic distance from aluminium to the nitrogen atom of
˚
N(1), is 2.737(3)A; a distance
N(C6H5)}]2Al{ONꢀC(CH3)C4H3S-2}×CH2Cl2
/
/
the oxime moiety, Al(1)ꢁ
/
that is sufficiently long to suggest there is no coordina-
tion. The bonds and angles within the ring systems are
essentially as expected and are listed as supporting data.
The structure of [C6H4O{CHꢀ
/
N(C6H5)}]2Al{ONꢀ
/
C(CH3)C4H3S-2} (10) consists of a discrete monomeric
unit with five coordination around the aluminium(III)
atom as shown in Fig. 4. The geometry around the
aluminium atom is a distorted trigonal bipyramid. The
aluminium atom lies within the plane in which the
equatorial positions are occupied by the oxygen atom of
the oxime, O(1), and those of the two N-phenylsalicy-
The molecular structure of [C6H4O{CHꢀ
/
N(C6H5)}]2-
Al{ONꢀ
/
C(CH3)C4H3S-2} 10 probably represents the
first known example of a five-coordinate heteroleptic
aluminium(III) compound.
lideneiminato bidentate ligands, O(2) and O(3). The Oꢁ
AlꢁO bond angles, which sum to 359.98, are all close to
1208, Table 9. The axial positions are occupied by the
/
/
4. Supplementary material
The crystal code for [C6H4O{CHꢀ
/
N(C6H5)}]2-
Al{ONꢀ CH2Cl2 is CCDC No.
/
C(CH3)C4H3S-2}×
/
192483. Supplementary data are available from the
Director, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax:
ꢃ44-1223-336033; e-mail: deposit@ccdc.cam.
/
ac.uk. or www: http://www.ccdc.cam.ac.uk) on request,
quoting the deposition number 192483. Additional
material available from the Cambridge Crystallographic
Data Centre comprises the final atomic coordinates for
all atoms, parameters, and a complete listing of bond
distances and angles.
Acknowledgements
One of us (N.S.) is grateful to CSIR for a senior
research fellowship. We are thankful to UGC, DST and
DAE for financial support. M.B.H. thanks the UK
Engineering and Physical Sciences Council for support
of the X-ray facilities at Southampton. J.E.D. thanks
the University of Windsor for financial support.
Fig. 4. ORTEP plot of the molecule [C6H4OCHꢀ
C(CH3)C4H3S-2}×CH2Cl2 1. The atoms are drawn with 30% prob-
ability ellipsoids and the atoms of CH2Cl2 are omitted for clearity.
/
NC6H5]2Al{ONꢀ
/
/

2952
N. Sharma et al. / Polyhedron 22 (2003) 2943ꢁ2952
/
[8] DENZO Z. Otwinowski, W. Minor, Methods in Enzymol, in:
C.W. Carter, Jr. R.M. Sweet, (Eds.), Macromolecular Crystal-
lography, Part A, 307; Academic Press, New York, 1997, p. 276.
[9] SORTAV, R.H. Blessing, Acta Crystallogr., A 51 (1995) 33; R.H.
Blessing, J. Appl. Crystallogr. 30 (1997) 421.
[10] G.M. Sheldrick, Acta Crystallogr. A 46 (1990) 467.
[11] L.J. Farrugia, J. Appl. Cryst. 32 (1999) 837.
[12] G.M. Sheldrick, SHELXL-97, University of Gottingen, Germany,
1997.
References
[1] N. Sharma, R.K. Sharma, R. Bohra, J.E. Drake, M.B. Hurst-
house, M.E. Light, J. Chem. Soc., Dalton Trans. (2002) 1631.
[2] N. Sharma, R.K. Sharma, R. Bohra, J. Chem. Res. (2003) in
press.
[3] A. Gupta, R.K. Sharma, R. Bohra, V.K. Jain, J.E. Drake, M.B.
Hursthouse, M.E. Light, J. Organomet. Chem. 645 (2002) 118.
[4] V. Sharma, R.K. Sharma, R. Bohra, R. Ratnani, V.K. Jain, J.E.
Drake, M.B. Hursthouse, M.E. Light, J. Organomet. Chem. 651
(2002) 98.
[13] A. Singh, A.K. Rai, R.C. Mehrotra, Indian J. Chem. 11 (1973)
478.
[14] B. Khera, A.K. Sharma, N.K. Kaushik, Polyhedron 2 (1983)
1177.
[5] V. Sharma, R.K. Sharma, R. Bohra, V.K. Jain, Main Group Met.
Chem. 25 (2002) 443.
[15] N. Dharmaraj, P. Viswanathamurthi, K. Natarajan, Trans. Met.
Chem. 26 (2001) 105.
[6] A.I. Vogel, Text Book of Quantitative Chemical Analysis, 5th ed.,
Longmans, London, 1989.
[16] N. Sharma, R.K. Sharma, R. Bohra, Main Group Met. Chem. 24
(2001) 781.
[7] D.C. Bradley, F.M.A. Halim, W. Wardlaw, J. Chem. Soc. (1950)
3450.